Production of resins by reaction of maleic anhydride with steam-cracked fractions



United States Patent PRODUCTION OF RESINS BY REACTION OF MA- LEICANHYDRIDE WITH STEAM-CRACKED FRACTIONS Egi V. Fasce, Baton Rouge, La.,assignor to Esso Research and Engineering Company, a corporation ofDelaware No Drawing. Application March 18, 1953 Serial No. 343,266

3 Claims. (Cl. 260-785) This invention is broadly concerned with thepreparation of new resins and, more particularly, is concerned with thecondensation of anhydrides with selected unsaturated hydrocarbonfractions to yield light colored, high melting, high quality resinstogether with the separation of concentrated hydrocarbon streams.

It is known that a number of chemical and petroleum processes result inthe production of hydrocarbon mixtures containing varying quantities ofolefins, both branched chain and straight chain, diolefins, aromatichydrocarbons, and paraflfiins, as well as other minor constituents.Processes which give such mixtures include catalytic and thermalcracking of petroleum feeds, steam cracking operations, vapor phasecracking and UOP non-, selective polymerization processes (see PetroleumRefiner (Process Handbook Edition), vol. 27: 124 (September 1948)).

Separation of the various components is very difficult and fineseparations are frequently impossible. Therefore, any process affordingefiicient utilization and separation of such mixtures is highlydesirable and valuable to the art.

There has now been discovered a method whereby, mixtures of hydrocarbonmaterials containing olefins of branched and straight chain types,diolefins, cyclic olefins, and aromatics can be treated in a series ofinterrelated and coacting steps to produce a stream containing thecomparatively valuable straight chain olefins, a stream containing thehighly useful cyclic olefins and aromatic' constituents, together withvaluable, light colored, high melting resins utilizing the branchedchain olefins and diolefins.

Thus, the invention is based on the fact that light colored resins,melting above 200 C. can be made by the condensation of maleic anhydridewith olefin and,

diolefin containing streams. The entire process to make the resins andisolate the separate streams includes the urea extraction whichsubstantially removes the-normal olefins and parafiins in the extractand also includes a maleic anhydride condensation of the rafiinateproducts to convert the branched chain olefins and diolefins intoresins. The unreacted material from this condensation is an aromaticconcentrate containing also the cyclic if desired, can be furthersubjected 'to purification steps much as selective crystallizationorsolvent.

olefins which,

extraction. Another method of operation includes carrying out the maleicanhydride condensation on the total stream by which the branched chainolefins and diolefins are removed as the resin product followed by aurea.

treatment of the rafiinate to separate the normal olefins;

The ral'linate from the urea treating step and paratfins. would consistof relatively pure aromatics together with' the cyclic olefins.

' Thegeneral. facts regarding urea extraction for separation betweennormal and branched chain olefins have been known. Under the'properreaction conditions urea will selectively combine with normal olefinsand parafiins to the substantial exclusion of combination with hydrocar-2,824,859 Patented Feb. 25, 1 958 ice bons of other types. It isbelieved that the urea and the reacting hydrocarbons form loosely boundcoordinated compounds of hydrocarbon with urea. The combination isusually referred to as complex formation. The extraction may be carriedout simply by contacting the hydrocarbon mixture to be separated withthe urea reactant. A solvent may be used, if desired, although it is notnecessary. The solvent chosen should be one in which both the normalhydrocarbons to be segregated and the urea are soluble. Suitablesolvents include the alcohols and the alcohol amines. Methanol has beenfound to be particularly suitable and convenient. Others include ethylalcohol, the propyl alcohols, the butyl alcohols, the amyl alcohols,ethanol amine, propyl amine, and diethanol amine. The amount of solventnecessary need not completely dissolve the urea and hydrocarbon treated.There should be enough solvent, however, to maintain the urea and thehydrocarbons as a slurry.

To summarize the urea extraction process, a mixture is made of the ureawith a mixture of hydrocarbons containing the normal aliphatic olefinsand paraffins to be separated. These reactants are then passed to areaction zone whereby the urea and normal olefin hydrocarbons presentreact to form solid addition compounds. These solid addition compoundsmay then be separated by a simple filtration, settling step, and theymay then be decomposed by the application of heat, or water to releasethe normal olefins. If a solvent such as methanol is employed, asomewhat lower temperature may be required to separate the crystals.

The cuts or fractious used as starting feeds in this process may varywidely as to the composition. The fractions may boil from 200 to 600 F.or be any fraction selected therefrom. In general, the more desirablefeeds are characterized by high olefin content, 50-80% consisting of5,l0% n-olefins, and the remainder 45-75% highly branched olefins aswell as 5-10% n-paraflins and the remainder largely substituted benzenesand polycyclic aromatics plus small concentrations of diolefins and somecyclic olefins.

For instance, the urea treating of a C to C distillate out is notcritical, any temperature in the range of about to 400 F. being quiteuseful. The period of time required is likewise not critical, but willdepend somewhat on the other conditions employed, particularly thetemperature. Time and temperature should be adequate topermitsubstantially complete reaction of the branched chain olefins withthe maleic anhydride. A solvent may be employed if desired although theuse of one is not necessary. Good agitation should be provided duringthe condensation reaction. Under the suitable conditions,

the branched chain olefins present in the naphtha react? quitecompletely with the maleic anhydride to form a light colored resinhaving a melting point above 200 C. This resin is separated, forexample, by filtration and the filtrate contains the concentratedaromatics which may.

later be separated, if desired.

Alternatively, theinitial stream may be treated with: mal'eicanhydrideto form the resin from the branched. procedure has been found to. resinproduct based on the hydro-;

chain constituents. This yield from 25 to 50% carbon cut employed. Theunreacted naphtha can then be subjectedto a urea extraction, if desired,-to'separate normal -oIfihsffom aromatics and cyclic olefins.

The resins which are prepared by this new method can be. used .in,coatingcompositions for preparing fioon tile;

1 Additionally, these resins. canfbe.subjectedftd further reactions tochange or modify their. properties. For example, .their properties canbe alteredbyconverting the anhydi'ide to an acid chloride witha suitableagent suchas thi'onyl'chloride andfthe-lik'e; .Tlie acid chlorile isthenfurth'er reacted with an. alcohol; such .asan aliphaticalcoholl'having oneiup toten or twelve carbon atoms for example,isooctyl alcohol." The resin diacid chloridesis thereby converted to thedi'octyl ester.

modifiers 'andlas chemical intermediates and reactants.

It is 'to 'be understood that the. foregoing operations can be carried'out either in'abatch or continuous. manner, the" exact manner in whichthe operation is done being unimportant." V The "inventionjwilfbedescribed in greater detail by the fdllowingexamples; although itisflnotintended to limit the-invention thereto; All parts" aresby weightunless otherwisenoted."

EXAMPLE. 1 p i 7 About 260 :parts of" the crude 305-355 F. "cut from asteamcracked distillate-cut, representing 12. 7% of the product,WastreatedrwithflOQparts'of maleic anh'ydride by refluxing, withagitation, at 300 F 5for two-hours; A vigorous'reaction:resulted withthe'appearance'of a' head the unreacted hydrocarbons and maleic,anhydride. The distillate consisted of a. total of 124 parts. Thedistillation bottoms represented a recovery of 137.5 parts of yellowbrown solid,re sin and corresponds to a net a yield of 53% by weight ofthe; combined charge.

Extraction of the distillate with caustic to rem oveithe unre'actedimaleicyanhydride yielded 108.5' parts%'ofa hy= drocarbon layer; waterwhite in color an'ck improved aromatic odor; This corresponds to 68%' ofth efeed.

Bydifference, approximately- 30% of the feed reacted to form the resinproduct.

EXAMPLE '3 s Urea: extraction: :studies were conducted on tli'e crude l5heavy naphtha feed rand*selected- 50 F. cuts from 350 F. to 570 F(Distill-ation data which are summarized in Table I indicate "that 85% ofthe product represents C C hydrocarbons, of'which more than :half

v for-63%-representsC C g hydrocarbonsa Urea extfae Such derivativesfinduse asplastlcizers, orlandgrease 20 fibndatwshowngbelowiin TabiHindiaterthafyieldgbf V a were obtained from' the crude naphtha feed. jThe oleifih constituents by infrared were]shownto'consist'predoihinat'ely of alpha-olefins. Further breakdown byextra -w tion of the350400, 400-'440-,-440-'498; nemia-554 1 3 cuts indicated yields of'9.8,'8.6 ,7.'9';"and"4.0% ofextrac't product of 40-49%: alpha-olefincontents. The urea constituents; Table! V V 'DISTILLATION OF'H'EAVYAPHTHK FEED,

solid insoluble-resinous productr 'Ahydrocarbon laye'r; V V Percent,pale-yellow in' color and-having anarornatie'odor. was z Weight f ldecante'd from the solid. resin; A net yield'-of*190 parts Pomp Percentplggofiiifigf of: crude-:resin-bottoms which. melts, above 200' ;C.'(4QQ'F;)-W8.S obtained; This vyield -corresponds.-to.53% 40 by: weightof: resin:' based on the combined charge-or Chmeg g 34.5% by weighhbasedonthe hydrocarbon feed; 7 e11 Saponification ofithe'resin'bottoms with10%"caustic 8 resulted in a light brown solution, which uponacidifica-251's tionwith hydrochloric acid'precipitated OIJlE a bulky light Rm'mmgig colored precipitate. The'r dry precipitate re'presen'ted a Table uCrude V 7 i Nlggeltlvt'ga Cut#3 :Qut cutfiz 01 11716 UieaEih-action marVol. PBICQHL.-; IOU; 200-600 25.4- .4 23i Extract Product: j Wt. PercentFeed.-.---.- .1 6.7 Gravity, "APII- 52.9

Bromine No; 47f

12;- n13 Ratfiuate Product: i V

'Wt. ereent Feed.-..- r 193."3=

Gravlty,APl 23.1. Bromine No 86'- Speclfic Dlspersion-.-- =168- 'aeisteam cracked'dis'tillat'e product'(129% by'wei'g'ht) was employed inthis condensation run." Thisfeed con-' tairted a -total of 73% olefinfrom'brominenumber deterw m iiiati'onzl 'The -feed'wasrefltixedfwith85iaartsfof maleic ahhy'dr ide for *twohour's: 'Theproduct at thefendofithe runxwas dis'ttlled' atatmospheric pressure totake oversecond stagefu'rea"extraction'filed to 'gi e m sfit,

stantiat addition'at'extraet; This indicates that the. single stageextraction lifocle'fssfgi es, essentially-complete .extr ace Te summarten is believed that the heayy naphthag feed, composed of 3.3% 1weight of; predominately a a 4 Herein reterr edstol art-:1 in subsequentgrefereuce ef ineludi meme 1 re resentvsteam"craeked distillate streamemploy as; feed Q tarelay? treating stepltor remover eedidlefln' con Vstituente;

C -C n-olefins, 3.4% of n-paraflins, 65-70% highly branched olefins anddiolefins, and 23-28% aromatics. A urea extraction of this feed gives asthe extract, an n-olefin-paraflin mixture containing from 40 to 50% ofEXAMPLE 5 Maleic anhydride condensation studies were carried out on aseries of feeds. These included the following:

(1) Steam cracked distillate 355 to 405 F. cut.

2 ig'g gggg :23 Z g z gig l gz g largely of branched 5 (2) Rafiinateproduct from urea extraction of the steam 0 This type of rafiinatereacts well with maleic anhygg g g z 355 ig dride to give a solid, highmelting resin product and an 4 C I .eavy 2 3 e 47'3c F unreacteddistillate fraction consisting substantially of the ata ytlc crac e toaromatics and unreacted cyclic olefins. (5) (3,12 polypropylene Plefin EL 4 The yields and properties of the respective resins and XAM Eunreacted hydrocarbon products from the above feeds Narrow boiling cuts(50 F.) on a distillate stream are summarizedinTable IV below.

Table IV Steam Cracked Rafiinate Product Catalytic Cracked Distillate355-405 F. from Urea Extrac- Heavy Naphtha N aphtha 408-473" F. 0Polypropylene Cut talgligslgifis tllats Feed Cut Out Feed:

Yield, Wt. PercentDistillate. 12.7 120 100 100. Gravity, API 28 r 24.4-25.4 31.3. 49.1. Bromine N o. 75 69 82 39 127. Percent Olefins 73(Cu)66w) 456312-015) Specific Dispersion 182 181 169 Maleic Anhydride Rosin:

Yield, Wt. Percent Hydro- 78 6 45.5 18 22.6.

carbon Feed. Resin Lt. Brown Solid Lt. Brown Solid Pale Yellow SolidVery Viscous Brown Clear Lt. Brown U eacted Hydr c rbon Resin. Resin.Resin. Resin- Viscous Polymer.

' Yield, Wt. Percent Hydro- 61.5 63 725 82 83. 7 carbon Feed. Gravity,API 31.8 26 7 48.9. Bromine Nor. 4L 46. 133. Percent olefins 40(Cu)44(Cn) Specific Dispersion. 161 181 Peg fem Aromatics (by 41 14 4.

product were also urea extracted. Fifty gallons of this EXAMPLE 6 V I yproduct was distilled in the 60 gallon still. The distilla- 40 In orderto alter and improve the properfis of these g gg g gz ig f i g g i i giiggggfi sfii resin products, an esterification was carried out withisotraction of the so s-sss $55 405-s" 1= cuts repurpose of preparmg.thsult'ed in respective olefin extract yields of 5 9 7 2 and faster a F ipbreparatmn of Y g is out me in a e co umn a ove, was emp oye Egg 92 i?g z g fi zgg g i g gg 22 335; 45 in the esterification reaction.Thirty-eight parts of the C C cuts The remainder of the Extract crudesolid resin together with about 200 parts of carbon ctiii stitii ntswere identified as n-paraflins. The olefin teirachloride solvent wereplaced in a reactor eqiuppfid constituents are largely (95 99% alphaolefins with with a stirrer and a reflux condenser. To the mixture,traces of aromatic hydrocarbons. The raifinate product 50 ag'tfited at-170 was i a one-hour comprises a mixture of largely (SO-60%) branchedchain Penod, 35 pafts offhfonyl chionde or a sllght excess to olefinsand diolefins and the remainder aromatic hydrofoml the deslredflacld Chlnde. The mlxture was recarbons. This feed, too, reacts well with maleicanhyl f f r l ad itional One-half hour. The mixture was dride to giveresins from the branched chain olefins and distilled until no furtherodor of thionyl chloride was an unreacted fraction containing thearomatics. 55 present in the overhead distillate.

Table III DIS'IILLATION OF STEAM CRACKED DISTILLATE Boiling Wt. Gravity,Bromine Wt. Specific Point, Percent API No. Percent Disper- F. ChargeOlcfins sion Charge 32 74 Out #1-- up to 55 "i5 "5516 III: "ii

plasticizing agent.

The residue in the flask vv'as' the e sterified by adding 0.5.: moleeofeiso-oct yl ralcoliol; The additioni'of thealcohol wasi'madeiover-a:one-houriiperiom -Refinxing:was a continued for an additionalhour. Th'e reactionmixture,

upon: cooling,- was filtered-to" separate-' 'ofl thei-solid materialby-product. V V V V The filtrate product Wasdistilled to remove "thefinal traces of solvent, andfunreactedfalcohol, first, bydistillation to300 F. at atmospheric pressure andfinally, to.2

to 3 millimeters. at maximum"bottoms-. temperature of 379 A tfi d, 3 933fv s a fi r s p i uid ester product representing 126% by weight oftheresin feed was obtained. The ester prodiictshovked the followingproperties:

is quite saturated and essentiallyanester:

Experimentstin plasticizlng were carried out on samples of the esterproduct in which blends 'of j5q%'fjofthejester-f"j resin product wascompatible withVinyI-resin-and-gaVeh a tough plastic thatdidnot" bl s ]we ibenti irtresei251i;

testsshow that the di-octyl resin product can be used as v aWhat'is-claimedis." j p 1.'A"separati0n process which comprisesextracting normal aliphatic olefins andparaflinsmontainedin-a-steairr-2,518,677?- Cracked P le m tra ion .bqi ngili tween .ahonL 20.0! L r r,and 600 F with urea and removing therefrom the resultf branched-chainolefins, aromaticrhvdrocarbons and cyelicv olefins; condensing thebranched-chain olefins and diole fins contained in' said 'r'affih'a'teWith "maric' 'a'riliydfide "at a temperature of at least F. and removingtherefrom the resulting condensate, and recovering the remainingaromatic hydrocarbonsand cyclic olefins.

2i "A process I according to claim 1 wherein said' urea is added insolution witha;solvent in Which'both said urea and said aliphaticolefins and .paraifins j are soluble. 7

31A separation process which comprises first'jcontacting'a C1 to'Csteamrcrackingldistillate fraction with urea in, an extraction zone,'se'paratingla hydrocarbon raf finate' containing'di'olfins,branched-chain olefins, aromatic hydrocarbons and cycliclolefins fromthe resulting addition compounds of th'e normalolefins andparafiinscombined with the urea, and decomposing said addition compounds torelease said normal olefins and parafiins; then contacting theraflinate, containing agsubstantial proportionpf branched chain olefinsand di0lefii1s,'vvith maleic anhyi meltr dride in a condensationreaction zone at a temperature in the range of about 75 to 400;F.,separating therefrom V the resulting light colored branched-chain resinhaving a V g point"above 2'0'0' C.; lastly, recovering the re-v*mainingiportioni ofisaidraflinate fraction consisting essen From theabove inspections, it is clear that the product 20 tial'lyfofgiaroniatic hydrocarbons and cyclic olefins not removei"RterncEsiCitd'infthelliledf tfiis 'patent:

' 5; UNITEDISTATESLPATENI'Si 21 20. 7k 2,527,o p I 2 15334 ,t a n nso ieOTHER"KEFERENCES' Heilbron; "Dictionary-"0f Grganic Compounds page 1865, item 2,4,4-trimethy1 l-pentene, Oxford University Press, New York(19 43), a

e' s F e ra t ve n? ssn e jet s steps for purifvin'g by" conventionalpurification means.

Aug-15,1950

1. A SEPARATION PROCESS WHICH COMPRISES EXTRACTING NORMAL ALIPHATICOLEFINS AND PARAFFINS CONTAINED IN A STEAMCRACKED PETROLEUM FRACTIONBOILING BETWEEN ABOUT 200* AND 600*F. WITH UREA AND REMOVING THEREFROMTHE RESULTING SOLID EXTRACT TO OBTAIN A RAFFINATE CONTAINING DIOLEFINS,BRANCHED-CHAIN OLEFINS, AROMATIC HYDROCARBONS AND CYCLIC OLEFINS,CONDENSING THE BRANCHED-CHAIN OLEFINS AND DIOLEFINS CONTAINED IN SAIDRAFFINATE WITH MALEIC ANHYDRIDE AT A TEMPERATURE OF AT LEAST 75*F. ANDREMOVING THEREFROM THE RESULTING CONDENSATE, AND RECOVERING THEREMAINING AROMATIC HYDROCARBONS AND DYCLIC OLEFINS.